Color photography



Patented Oct. 18, 1938 UNITED STATES,

PATENT OFFICE COLOR PHOTOGRAPHY Edmund B. Middleton and Andrew B.Jennings,

New Brunswick, N. Film Manufacturing assignors to Du Pont I a.

rporation, New York,

N. Y., acorporation of Delaware No Drawing. Application February 15,1937, Serial No. 125,894

21 Claims. (on. 95-88) vide a color-photographic element derived fromcolor-forming compounds which, in combination a with certain classes ofdeveloping agents, will form dyes in situ with photographic images. Afurther object is to produce such dyes by colorforming development.Another object is to produce partial color-records in which theindividual records are of improved spectral quality for colorphotography.

It has been formerly taught to prepare colored photographs by developingexposed silver salt emulsion layers in certain developing agents whoseoxidation products are water-insoluble dyes. Thus, a silver halidelayer, bearing a latent image, can be developed in an alkaline indoxylsolution, whereupon a silver image is produced along with a blue dyeimage in situ with the silver. The silver image can be removed byFarmers Reducer revealing the dye image. In like manner, a photographicrecord can be developed in chlor-indoxyl to produce a green image and inthio-indoxyl for a red image.

It is also known, for the purposeof preparing color pictures, to developexposed silver halide layers by agents whose oxidation products are notcolored but which will chemically unite or couple with other organicagents, called colorformers to form intensely colored dyes. Thesecolor-formers are not photographic developers, are generallywater-insoluble and produce dyes in situ with, and simultaneously withthe deposition of the metallic silver image. The developers used forthese proposed processes are of the diamino-aryl class, such asparaphenylendiamine' or its substitution products, such as for example,di-methyl or di-ethyl-para-phenylene-diamine. Color-forming compoundsalready proposed include, for example, thymol, benzoyl acetone, phenacylchloride and para-nitrobenzyl cyanide.

These prior processes, however, have failed to produce colored imageshaving the correct spectral qualities for color photography. Moreover,these prior color-formers tend to have a harmful eflect on thesensitivity of silver halide emulsions, so that, for these reasons, thecolor-formers already known have not provided a practical means forcolor photography.

The present invention has demonstrated thatacylacetaminoarylmorpholines, in conjunction with aromatic aminodeveloping agents, form satisfactory dye images. Theacylacetamino-arylmorpholines are aminoarylmorpholines wherein an aminohydrogen is replaced by the radicle of an acyl acetic acid, e. g.,acetoacetic acid,

malonic acid, cyanacetic acid, furoylacetic acid, benzolylacetic acidand naphthoylacetic acid. The aminoarylmorpholines include theorthometa-and para-aminophenylmorpholines, aminophenylthiomorpholines,aminonaphthylmorpholines, aminonaphthylthiomorpholines and theirsubstitution products.

Aoeto-aoet-p-aminopbcuylmorpholine HN.COCH:.OOCHI N J H, d: H;

H: H: Aoeto-acet-4-amino-2-5-diethoxy-phenyl-morphoiine HN.COOH1.COCH|Acoto-acet-p-amino-m-chlor-phonyl-morpholino HI|-I.COCH;.COOH;

N C H1 Cm (5H1 3H2 Aoeto-aoeto-p-amino-phenyl-thiomorpholiueHN.COCH:.COCH;

N :21: 1 on E \Q/ g The preferred color-formingcompounds above describedmay be used either in developers or as an addition to silver halideemulsions.

As preferred color-forming developers, the following produce excellentresults:

Formula 1 i Diethyi-p-phenylenediamine hydrochloride 2 gm" Sodiumsuiiite, anhydrous gm 5 Sodium carbonate, anhydrous -gm wat to liter 1To which is added aceto-acet-p-amino- I phenyl morpholine gm 1.0 Ethylal 00.; 100

Formula 2 Diethyl-p-phenylenediamine hydrochloride I gm 2 Sodiumsulflte, anhydrous gm 5 Sodium carbonate, anhydrous gm 20 Water to liter1 To which is added aceto-acet-4-amino-2-5- diethow-phenyl-morpholine gm1.0 lithyl alc cc 100 In place of the di-alkyl-substitutedp-phenylenediamine, the mono-alkylated substitution produce may be usedor the un-substituted p-phenylenediamine may be' used as well as thebases and/or acid salts of these developing agents. In place of theethyl alcohol, methyl alcohol or acetone may be used, and, if desired,the organic solvent for the color-forming compound may be dispensed withentirely. A

If it is desired to add the color-forming compound directly to theemulsion, a preferred procedure is as follows: 10 grams of the color-!ormer is dissolved in 200 mls. of ethyl alcohol 'to which is addedabout 50 grams of gelatin in 500 mls. of water and then thoroughlymixed.

This color-forming solution is then added, with vigorous stirring, to 1liter of silver-gelatinoemulsion. Emulsions containing thesecolorforming compounds may be coated as layers on one or both sides of aphotographic support either as individual or superposed emulsion layers.

While it is preferred to employ silver-gelatinoemulsions, otheremulsions comprising other well known sensitizers and binding agents mayalso be used. Examples of these are the well known silver collodionemulsion, albuminoid emulsion, or bichromated emulsion.

In the form of color-forming developers, the above described compoundsmay also be used to re-develop bleached silver images. Thus, a silverimage may be bleached in potassium ferrocya-' nide or a mixture ofchromic and hydrobrornic acids and re-exposed, whereupon the bleachedimage can be re-developed to silver and a dye image by the color-formingdevelopers above described. After development, the silver is removed byany of the well known reducers such as Farmers Reducer.

While the foregoing specification sets forth the preferredexempliilcations of the present invenline.

2. A color-forming photographic developer comprising an aromatic aminophotographic developing agent and an acetoacetaminoarylmorpholine. 3. Acolor-forming photographic developer comprising an aromatic aminophotographic developing agent and an acylacetaminophenylmorpholine.

4. A color-forming photographic developer comprising an aromatic aminophotographic developing agent and an acetoacetaminophenylmorpholine.

5. A color-forming photographic developer comprising an aromatic aminophotographic de- 12. A color-forming photographic emulsion comprising abinding agent, ahalogen salt of .silver and anacetoacetaminoarylmorpholine.

13. A color-forming photographic emulsion comprising a binding agent, ahalogen salt of silver and an acylacetaminophenylmorpholine.

14. A color-forming photographic emulsion comprisinga binding agent, ahalogen salt of silver and an acetoacetaminophenylmorpholine.

15. A color-forming photographic emulsion comprising a binding agent, ahalogen salt of silver and acetoacet-p-aminophenylmorpholine.

16. A color-forming photographic emulsion comprising a binding agent, asilver halide and an acetoacet 4. amino-2,5-diethoxyphenylmorpholine.

17. A color-forming photographic emulsion comprising a binding agent, asilver halide and {in acetoacet-p-amino 2 chlorophenylmorphono.

18. A color-forming photographic layer comprising a sensitizedgelatino-silver-halide emulsion and an acylacetaminoarylmorpholine.

19. A color-forming photographic layer comprising a sensitizedgelatino-silver-halide emulsion and an acetoacetaminoarylmorpholine.

20. A color-forming photographic layer comprising a sensitizedgelatino-silver-halide emulsion and an acylacetaminophenylmorpholine.

21. A color-forming. photographic layer comprising a sensitizedgelatino-siiver-halide emulsion and an 'acetoacetaminophenylmorpholine.

22. A color-forming photographic layer comprising a sensitizedgelatino-silver-halide emulsion and acetoacet-p-aminophenylmorpholine.

23. A color-forming photographic developer comprising anN-di-alkyl-p-phenylene diamine and an acylaoetaminoarylmorpholine.

24. A color-forming photographic developer comprising anN-di-alkyl-p-phenylene diamine and an acetoacetaminoarylmorpholine.

25. A color-forming photographic developer 27. A color-formingphotographic developer comprising an N-di-alkyl-p-phenylene diaminecomprising an N-di-alkyl-p-phenylene diamine and anacylacetaminophenylmorpholine. and acetoacet-p-aminophenylmorpholine.26. A color-forming photographic developer 5 comprising anN-di-alkyl-p-phenylene diamine EDMUND B. MIDDLETON.

and an acetoacetaminophenylmorpholine. ANDREW B. JENNINGS.

